Miniaturized liquid chromatography in environmental analysis. A review.

The greater and more widespread use of chemicals, either from industry or daily use, is leading to an increase in the discharge of these substances into the environment. Some of these are known to be hazardous to humans and the environment and are regulated, but there is a large and increasing number of substances which pose a potential risk even at low concentration and are not controlled. In this context, new techniques and methodologies are being developed to deal with this concern. Miniaturized liquid chromatography (LC) emerges as a greener and more sensitive alternative to conventional LC. Furthermore, advances in instrument miniaturization have made possible the development of portable LC instrumentation which may become a promising tool for in-situ monitoring. This work reviews the environmental applications of miniaturized LC over the last 15 years and discusses the different instrumentation, including off- and on-line pretreatment techniques, chromatographic conditions, and contributions to the environmental knowledge.

Portable determinations for legislated dissolved nitrogen forms in several environmental water samples as a study case.

In this work, we have studied the main species involved in determining total dissolved nitrogen (TDN) in water samples for accommodating a variety of quantitation methodologies to portable instruments and with the goal to achieve in situ analysis. The rise of water eutrophication is becoming an ecological problem in the world and TDN contributes markedly to this. Traditionally the several forms of DN are measured in the laboratory using conventional instrumentation from grab samples, but their analysis in place and in real time is a current demand. Inorganic nitrogen: NO3-, NO2- and NH4+, and organic nitrogen, such as amino nitrogen were tested here. For nitrate that presents native UV absorption suitable for direct water analysis, a portable optical fiber probe was compared with benchtop equipment and an in place analyzer. For nitrate, nitrite and ammonium, in situ solid devices that deliver reagents needed were tested and water color was measured by a smartphone coupled with a miniaturized optical fiber spectrometer and a miniaturized spectrometer or from images obtained and their RGB components. Amino nitrogen of some aromatic aminoacids with native fluorescence was followed by a portable optical fiber probe. Organic amino nitrogen and ammonium were determined by a portable luminometer and luminol supported in a measurement tube. Moreover, a portable miniaturized liquid chromatograph was shown suitable for monitoring priority nitrogen environmental pollutants. All options provided suitable results in comparison with lab estimations and were useful for evaluating if the legislation is fulfilled for the variety of tested waters. A discussion about the several portable options proposed for in place analysis, in function of the legislated determinations needed for each type of water was carried out.

Towards in field miniaturized liquid chromatography: Biocides in wastewater as a proof of concept.

Solving and/or evaluating given problems or decision making in place and in real time is a goal of the analytical chemistry science. In this context, the performance of a commercial portable miniaturized liquid chromatograph (minLC) with LED UV (255 nm) detector was compared with those provided by two lab minLCs (capillary and nano) coupled on-line to in-valve in-tube solid phase microextraction (IT-SPME) with diode array detector (DAD). In addition, responses of the portable LC for in-field analysis in several conditions were tested. Besides, two evaluation tools, BETTER criteria for portability and HEXAGON pictogram for sustainability and greenness were applied for comparison purposes. The benchtop LCs provided lower limits of detection (LODs) as expected, in the order of low µg L-1, than those achieved by the portable LC, with LODs around mg L-1 for compounds covering several polarities (logKow between -1.72 and 3.82). The used portable LC gave excellent resolution, reducing the analysis time and being the consumption of solvents negligible. As a practical application, fruit washing residual waters, which contained a suitable level of concentrations of several biocides for employing the portable minLC, were analyzed and quantified from the three minLCs as a proof of concept with comparable results.

In-tube solid phase microextraction coupled to miniaturized liquid chromatography for both, noble metal nanoparticle assessment and sensitive plasmonic assay development.

Colorimetric localized surface plasmon resonance (LSPR) as analytical response is applied for a wide number of chemical sensors and biosensors. However, the dependence of different factors, such as size distribution of nanoparticles (NPs), shape, dielectric environment, inter-particle distance and matrix, among others, can provide non-reliable results by UV-vis spectrometry in complex matrices if NP assessment is not carried out, particularly at low levels of analyte concentrations. Miniaturized liquid chromatography, capillary (CapLC) and nano (NanoLC), coupled on line with in-tube solid phase microextraction (IT-SPME) is proposed for the first time for both, controlling suitability of used noble metal NP dispersions and developing plasmonic assays. Several capped noble NPs and target analytes were tested from variations in the chromatographic profiles obtained by using diode array detection. The IT-SPME step, which influenced the chromatographic fingerprint provided by noble NP dispersions, was studied by asymmetrical flow field flow fractionation (AF4) too. We monitored NP aggregation induced by interaction with several analytes like acids and spermine (SPN). Assessment of NPs was achieved in less than 10 min and it permitted to develop suitable plasmonic tests. Here, it was also demonstrated that these assays can be followed by IT-SPME-miniaturized LC-DAD and more sensitivity and selectivity than those provided by UV-Vis spectrometry were achieved. Analysing urine samples to determine SPN as a cancer biomarker as a proof of concept is presented.